EP1041050A1 - Grey glass composition and method of making same - Google Patents
Grey glass composition and method of making same Download PDFInfo
- Publication number
- EP1041050A1 EP1041050A1 EP00105978A EP00105978A EP1041050A1 EP 1041050 A1 EP1041050 A1 EP 1041050A1 EP 00105978 A EP00105978 A EP 00105978A EP 00105978 A EP00105978 A EP 00105978A EP 1041050 A1 EP1041050 A1 EP 1041050A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- glass
- prebatch
- less
- ingredient
- measured
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011521 glass Substances 0.000 title claims abstract description 141
- 239000000203 mixture Substances 0.000 title claims description 70
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000004615 ingredient Substances 0.000 claims abstract description 48
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000002834 transmittance Methods 0.000 claims abstract description 28
- 229910052742 iron Inorganic materials 0.000 claims abstract description 26
- 239000003086 colorant Substances 0.000 claims abstract description 22
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004576 sand Substances 0.000 claims abstract description 15
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 4
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 230000005284 excitation Effects 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 229910052684 Cerium Inorganic materials 0.000 claims description 11
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 229910052711 selenium Inorganic materials 0.000 claims description 8
- 239000011669 selenium Substances 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 6
- 239000006105 batch ingredient Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 235000017550 sodium carbonate Nutrition 0.000 claims description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 235000019738 Limestone Nutrition 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 239000010459 dolomite Substances 0.000 claims description 4
- 229910000514 dolomite Inorganic materials 0.000 claims description 4
- 239000006028 limestone Substances 0.000 claims description 4
- 239000005361 soda-lime glass Substances 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- PGPKUDCUWKDIIC-UHFFFAOYSA-N erbium(3+) iron(2+) oxygen(2-) Chemical compound [O-2].[Er+3].[O-2].[Fe+2] PGPKUDCUWKDIIC-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- 239000010936 titanium Substances 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 46
- 239000003638 chemical reducing agent Substances 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910000906 Bronze Inorganic materials 0.000 description 5
- 239000010974 bronze Substances 0.000 description 5
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 229910001448 ferrous ion Inorganic materials 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000005368 silicate glass Substances 0.000 description 3
- 238000006124 Pilkington process Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 239000000156 glass melt Substances 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- ZXGIFJXRQHZCGJ-UHFFFAOYSA-N erbium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Er+3].[Er+3] ZXGIFJXRQHZCGJ-UHFFFAOYSA-N 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- -1 rouge) Chemical compound 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/02—Compositions for glass with special properties for coloured glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
- C03C4/082—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for infrared absorbing glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
- C03C4/085—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for ultraviolet absorbing glass
Definitions
- This invention relates to grey glass compositions and methods of making same. More particularly, this invention relates to erbium-containing grey glass compositions having low light transmittance in the UV and IR range while, at the same time, having high light transmittance in the visible range, thus making such glasses suitable for use as windows and windshields in the automotive industry and architectural field, as well as, in certain embodiments, as eyeglass lenses.
- a glass window, windshield or other glass article is said to have the desirable color "grey", sometimes referred to as “neutral grey", if it manifests a dominant wavelength from about 435nm, and preferably from about 470nm, to less than about 570nm, in combination with an excitation purity of less than about 4.5%. This, then, defines the meaning of the term “grey” as used herein.
- a still more preferred range of dominant wavelength, thus defining a more preferred “grey” as used herein, is about 480nm - 550nm, and in like manner, a more preferred range of purity is about 0.2 - 4.5%.
- the term "a nominal thickness of about 1mm - 6mm,” and in certain embodiments, "about 3mm - 4mm” means that the characteristics of the glass are those experienced when the thickness of the actual glass under investigation is adjusted for that nominal thickness range.
- Such thickness ranges are generally recognized as conventional thicknesses for glass sheets made by the float glass process, as well as a recognized thickness range for the automotive industry.
- Luminous transmittance (LTa) [2° observer] is a characteristic and term well understood in the art, and is used herein in accordance with its well known meaning [see U.S. Patent No. 5,308,805]. This term is also known as Ill. A visible transmittance (380 - 780 nanometers inclusive), and its measurement is made in accordance with CIE Publication 15.2 (2986) and ANSI test method Z26.1.
- %UV Ultraviolet transmittance
- %IR Infrared transmittance
- Dominant wavelength (DW) is calculated and measured conventionally in accord with the aforesaid CIE Publication 15.2 (1986) and ASTM: E 308-90. Its calculation and measurement are also well known in the art. As used herein, therefore, the term “dominant wavelength” includes both the actual measured wavelength and, where applicable, its calculated complement.
- the glass For automotive windows (including windshields) it is desirable that the glass have the following characteristics (when measured at a nominal thickness of about 3mm - 4mm and preferably at about either 3.2 mm or 4mm as the particular situation may require), and often in the ultimate product as well:
- cerium being a well known UV absorber when present in glass in its reduced form, Ce 3+ , should be avoided for the following reason.
- Iron is conventionally introduced into glass in the form of Fe 2 O 3 , part of which should be reduced to FeO to achieve the requisite low IR transmittance value.
- Cerium which is introduced into glass in the form of CeO 2 , is known to oxidize divalent iron to trivalent iron either directly or by competition with any reducing agent present in the glass melt. Therefore, coexistence of iron oxide and cerium oxide will inevitably lead to a decrease in the concentration of FeO in the glass and thus will reduce its IR absorbing power.
- the aforesaid Japanese Patent No. 280834 employs Er 2 O 3 in a glass composition which is then said to have a "low thermal expansion coefficient."
- the glass employs from 10-20% B 2 O 3 and thus is properly referred to as a borosilicate glass, rather than the more conventional soda-lime-silica glasses used in automotive windows. While stating, in effect, that cobalt and nickel are optional, and no use of Se or Ce is reported, the dominant wavelength reported is accordingly rather high, i.e. from 570 - 610nm, or tending toward an objectionable bronze color, even at the lower wavelengths achieved, rather than achieving a true "grey" color as defined above.
- this invention fulfills the above-described needs in the art by providing a unique glass composition, glass articles made therefrom, and a unique method of making the glass.
- the unique glass compositions are comprised of a colorant portion consisting essentially of, by weight percent: Ingredient Approximate Wt.% Fe 2 O 3 (total iron) about 0.5 - 0.8% FeO about 0.1 - 0.25% Er 2 O 3 about 0.5 - 3.0% TiO 2 about 0 - 1.0% wherein the glass when measured at a nominal thickness of about 1mm - 6mm, and preferably about 3mm - 4mm (e.g. at 3.2mm and 4mm) has a dominant wavelength of from about 435nm to less than about 570nm and an excitation purity of less than about 4.5%.
- the above-described glasses having the aforesaid unique colorant portion it is preferred to include within the batch ingredients, and thus during glass formation, a reducing agent of one or more ingredients.
- the reducing agent is comprised of (by weight of the batch) about 0.01 - 0.3 wt.% of silicon monoxide (SiO) and about 0 - 0.12 wt.% of metallic silicon (Si).
- the reducing agent may be selected from one or more conventional glass melt reducers such as sucrose, tin, carbon, or the like.
- the combination of two lower valency forms of silicon namely, one agent (optional) in the form of metallic silicon (Si°) powder, and the other, (Si 2+ ) in the form of silicon monoxide (SiO), is utilized for the purpose of reducing the ferric ion to the ferrous ion, thereby obtaining a true "grey" glass with the requisite low IR transmittance as well as low UV and high visible transmittances, but without the necessity of the use of cerium.
- the preferred glasses of this invention are free of any cerium (except perhaps for an inadvertent trace amount in some instances).
- Si/SiO as the reducing agent is that during glass melting both agents are converted into SiO 2 , i.e. the main component in the preferred silicate glass matrices employed herein, without the need to add any dopant or other residue to the glass.
- certain unique glass compositions as contemplated by this invention comprise by weight percent: Ingredient Wt. % SiO 2 about 65 - 75 Na 2 O about 10 - 15 CaO about 1.5 - 15 MgO about 0 - 10 Al 2 O 3 about 0 - 3 K 2 O about 0.1 - 1 SO 3 about 0.1 - 0.3 TiO 2 about 0 - 1.0 Fe 2 O 3 about 0.50 - 0.80 FeO about 0.10 - 0.25 Er 2 O 3 about 0.50 - 3.0 B 2 O 3 about 0 - 12.0
- compositions are substantially free of one or more of Ce, Co, Se and Ni.
- the compositions are substantially free of all of these elements.
- substantially free is meant that such an element does not exist in an amount greater than a "trace amount” (i.e.usually as an impurity) and is not purposely added to the mix.
- the approximate upper limit for each element is as follows and below which the element is generally considered to be present only in a "trace amount”.
- the glass is entirely free of any measurable amount of such elements: Element Wt. of Glass (“trace amount”) cerium less than about 0.0020% cobalt less than about 0.0003% nickel less than about 0.0005% selenium less than about 0.0003%
- this invention may be said to achieve its true "grey” color by recognizing (and utilizing) the known principle of color formation that an achromatic (grey) glass can be obtained by the interference of only two colors, blue and pink, which if properly done, is more appealing aesthetically (as a true "grey” color) than the so-called “grey” colors heretofore achieved with combinations of colorants such as Se, Co, and Ni in combination with the background of blue color given by the ferrous ion in the glass.
- the very pure hue of light blue is obtained in the glass by the appropriate reduction of Fe 2 O 3 to FeO (the IR absorber).
- TiO 2 is an optional colorant and thus its amount of about 0.0% - 1.0% is included in this term to demonstrate that TiO 2 is contemplated as an affirmative colorant which optionally may be used above a trace amount.
- the preferred glasses according to this invention generally exhibit, in combination, the following characteristics as measured at their intended nominal thickness:
- the glasses of this invention find unique application in the automotive industry, they may also be used as flat glass for the architectural market for both single sheet windows and dual pane windows known as I.G. units. They may also be used as eyeglass lenses.
- windshield W front side windows F and rear side windows R are illustrated for areas of use for the glasses of this invention.
- Rear windows (sometimes called “backlights") are also applicable, but are not shown for convenience.
- a typical house H is schematically shown with a conventional window P having a glass sheet or sheets (when an I.G. unit) formed of a glass according to this invention.
- eyeglasses E are provided with a pair of lenses L made of a glass according to this invention.
- the glasses of this invention find utility wherever truly "grey” glasses having low UV and IR transmittances, as usually high LTa's, are desired or required.
- the preferred glasses for use in this invention employ conventional soda-lime-silica flat glass as their base composition, to which is then added certain ingredients to make up a unique colorant portion.
- various soda-lime-silica glasses used in making glass sheets by the float process and generally represented, conventionally, on a weight percent basis, as comprised of the following basic ingredients: Ingredient Wt. % SiO 2 68 - 75 Na 2 O 10 - 18 CaO 5 - 15 MgO 0 - 5 Al 2 O 3 0 - 5 K 2 O 0 - 5
- the glasses herein include by weight about 10-15% Na 2 O and 6-12% CaO.
- B 2 O 3 synergistically modified the absorption power of the ferrous and ferric iron, thereby achieving lower levels of UV, T s and IR transmittances than would otherwise be expected from such a relatively low amount of iron.
- This synergism is employed in certain embodiments of this invention as an enhancing factor to UV, IR and T s transmittances in order to minimize these transmittances without the use of cerium oxide or other known UV or IR absorbers.
- small amounts of TiO 2 are optionally employed to further limit UV absorption.
- the glasses of this invention achieve a true grey (or “neutral grey”) color, as opposed to manifesting an objectionable “bronze”, “blue grey” or “green grey” color.
- a true “grey” color is best defined, as aforesaid, by referring to the two characteristics of: (1) “dominant wavelength”, and (2) “excitation purity.” Also complementing this definition is reference to the aforesaid CIE LAB coordinates [Ill. C 2° observer].
- the glasses herein are true "grey” glasses because they have a dominant wavelength of from about 435nm to less than about 570nm, and most preferably between about 480nm - 550nm; coupled with an excitation purity less than about 4.5% and preferably from about 0.2% to about 4.5%.
- Such glasses will preferably also include the following CIE LAB color coordinates [Ill. C 2° observer] when measured at a nominal thickness of from about 1mm - 6mm (and preferably for most uses, at about 3mm - 4mm):
- the glass articles of this invention When used in the automotive market for windows and/or windshields that must conform to certain minimal visible light transmission properties (i.e. as measure as aforesaid as "Lta”), the glass articles of this invention will normally have an Lta at least equal to and preferably greater than about 70% and, in certain embodiments, greater than about 72%, and in still further instances, greater than 73%.
- the glasses of this invention achieve the above unique characteristics, particularly, for example, in silicate glasses, and more particularly in glasses of the soda-lime-silica type as defined above, as well as in borosilicate glasses, by the use of a unique colorant portion which includes a relatively high amount of iron in combination with erbium oxide (Er 2 O 3 ) and only, optionally, a small amount of TiO 2 , to the exclusion of anything but, at most, trace amounts of Ce, Se, Co and Ni.
- erbium oxide Er 2 O 3
- the colorant portions contemplated by this invention consist essentially of, by weight percent (of the total glass composition): Ingredient Wt.% Fe 2 O 3 (as total iron) about 0.5 - 0.8% FeO about 0.1 - 0.25% Er 2 O 3 about 0.5 - 3.0% TiO 2 about 0.0 - 1.0%
- the colorant portion of the glasses contemplated herein consist essentially of, by weight percent (of the total glass composition): Ingredient Wt. % Fe 2 O 3 (as total iron) about 0.6 - 0.8% FeO about 0.16 - 0.25% Er 2 O 3 about 1.0 - 2.0%
- the glasses will also include about 0.25 - 2.0 weight % B 2 O 3 , and preferably about 0.25 - 1.0% weight % B 2 O 3 , thereby achieving the heretofore known synergistic enhancing effect discussed above, but without adversely affecting color.
- Certain preferred glass compositions of this invention are generally classifiable as soda-lime-silica glasses, and in certain preferred embodiments include by weight percent about 10-15% Na 2 O and about 6-12% CaO. Still further embodiments include high levels of B 2 O 3 up to about 12% by weight, and such glasses are then properly referred to as being in the borosilicate family of glasses.
- Still further preferred glass compositions of this invention generally consist essentially of, by weight percent: Ingredient Weight % SiO 2 about 65 - 75 Na 2 O about 10 - 15 CaO about 1.5 - 15 MgO about 0 - 10 Al 2 O 3 about 0 - 3 K 2 O about 0.1 - 1 SO 3 about 0.15 - 0.25 TiO 2 about 0 - 1.0 Fe 2 O 3 about 0.50 - 0.80 FeO about 0.10 - 0.25 Er 2 O 3 about 0.50 - 3.0 B 2 O 3 about 0 - 12.0
- the glasses of this invention may be made from standard batch ingredients using well known glass melting and refining techniques once given the above final glass analysis.
- a typical batch example would be as follows, based upon a total of 100 parts by weight: Batch Ingredient Parts by Wt. sand about 70-73 soda ash about 20-26 dolomite about 16-19 limestone about 5.5-6.8 boric acid about 0.5-21 salt cake about 0.2-0.7 rouge (Fe 2 O 3 ) about 0.5-0.8 titania about 0.1-1.0 erbium oxide about 0.5-3.0 Si (metal) about 0.01-0.12 SiO about 0.02-0.3
- one of the prebatch mixes should be made up of the iron-containing ingredient (e.g. rouge) along with SiO (silicon monoxide) and optionally, metallic Si (i.e. the reducing agents), and preferably some of the sand.
- the total amount of the iron (e.g. rouge), metallic Si, and SiO are used in this first prebatch mix with a small amount of sand and are thoroughly mixed together separately from the remaining batch ingredients. It is preferred that, for example, on the basis of a total of 70-73 parts of sand by weight per hundred in the overall batch, only about 5-13 parts of sand is used in this first prebatch mix.
- the remaining batch ingredients can then be made up by admixing them in another separate prebatch mix or into two or more prebatch mixes before admixing them with the iron and reducing agent-containing first prebatch mix.
- the remaining ingredients are formed into two additional prebatch mixes.
- the first additional prebatch mix i.e. the second prebatch mix
- the second additional prebatch mix is then made up of the remaining ingredients which thus normally includes the rest of the sand (e.g. 60-65 parts and preferably about 61.5 parts, per hundred) and soda ash, and all of the dolomite, limestone, boric acid and salt cake to be used in the final batch.
- each separate prebatch mix is thoroughly separately mixed, to form a substantially homogenous powdered admixture
- the two or more prebatch mixes are then thoroughly mixed together to form the overall (or final) batch mixture.
- Conventional melting and refining techniques are then used to form a molten glass from which flat sheet glass or other articles may be formed.
- this multi-prebatch technique procedure of isolating and thoroughly mixing the iron, silicon monoxide and silicon metal in a separate prebatch mix leads to the formation of aggregates, or "clusters" in the batch, which form a "quasi-ingredient" of the batch.
- This quasi-ingredient then comprises all the “participants” (i.e. Fe 2 O 3 , SiO and Si "dissolved” in a small amount of sand) of the above-described reactions of reduction of ferric ion to ferrous ion by the two lower valence forms of silicon.
- Glass samples having the composition and properties shown in the TABLE below were formed from the ingredients listed in the first columns of this table, using the three prebatch mixing technique as described above.
- the ingredient listed as "Fe 2 O 3 " is total iron and was added as conventional rouge to the first prebatch which also included metallic silicon (when used), silicon monoxide, and a portion (5-13 parts per hundred) of the total sand.
- the second prebatch then included the erbium oxide, titania (when used), and about one-third of the total soda ash employed.
- the third prebatch included the remainder of the ingredients as listed.
- the three prebatch mixes were then mixed together to form the overall batch mixture.
- the overall batch mixture was then melted in an electric furnace in a conventional crucible at a temperature in the range between 1480° and 1520°C.
- the molten glass was then cast into molds for measurement sampling (e.g. 2" diameter buttons), annealed at 620°C. for 1/2 hour and cooled to room temperature.
- the cooled glass was polished to prepare either 4mm or 3.2mm thick specimens which were then measured using conventional practices as described above.
Abstract
Description
- LTa
- as visible light transmission,
- UV
- as ultraviolet light transmission,
- IR
- as infrared light transmission, and
- Ts
- as total solar transmission.
- LTa,
- greater than about 70%
- UV,
- less than about 42%, preferably less than about 38%
- IR,
- less than about 37%, preferably less than about 28%
- Ts,
- less than about 47%.
Ingredient | Approximate Wt.% |
Fe2O3 (total iron) | about 0.5 - 0.8% |
FeO | about 0.1 - 0.25% |
Er2O3 | about 0.5 - 3.0% |
TiO2 | about 0 - 1.0% |
Ingredient | Wt. % |
SiO2 | about 65 - 75 |
Na2O | about 10 - 15 |
CaO | about 1.5 - 15 |
MgO | about 0 - 10 |
Al2O3 | about 0 - 3 |
K2O | about 0.1 - 1 |
SO3 | about 0.1 - 0.3 |
TiO2 | about 0 - 1.0 |
Fe2O3 | about 0.50 - 0.80 |
FeO | about 0.10 - 0.25 |
Er2O3 | about 0.50 - 3.0 |
B2O3 | about 0 - 12.0 |
Element | Wt. of Glass ("trace amount") |
cerium | less than about 0.0020% |
cobalt | less than about 0.0003% |
nickel | less than about 0.0005% |
selenium | less than about 0.0003% |
Ingredient |
sand |
iron oxide |
erbium oxide |
metallic Si |
SiO (silicon monoxide) |
Ingredient |
iron oxide |
metallic Si |
SiO (silicon monoxide) |
sand |
Ingredient | Wt. % |
SiO2 | 68 - 75 |
Na2O | 10 - 18 |
CaO | 5 - 15 |
MgO | 0 - 5 |
Al2O3 | 0 - 5 |
K2O | 0 - 5 |
- L*
- about 86 - 91
- a*
- about -2.4 to +1.6
- b*
- about -5.0 to +2.0.
- L*
- about 87 - 89
- a*
- about -0.5 to +1.0
- b*
- about -3.0 to -1.0.
Ingredient | Wt.% |
Fe2O3 (as total iron) | about 0.5 - 0.8% |
FeO | about 0.1 - 0.25% |
Er2O3 | about 0.5 - 3.0% |
TiO2 | about 0.0 - 1.0% |
Ingredient | Wt. % |
Fe2O3 (as total iron) | about 0.6 - 0.8% |
FeO | about 0.16 - 0.25% |
Er2O3 | about 1.0 - 2.0% |
Ingredient | Weight % |
SiO2 | about 65 - 75 |
Na2O | about 10 - 15 |
CaO | about 1.5 - 15 |
MgO | about 0 - 10 |
Al2O3 | about 0 - 3 |
K2O | about 0.1 - 1 |
SO3 | about 0.15 - 0.25 |
TiO2 | about 0 - 1.0 |
Fe2O3 | about 0.50 - 0.80 |
FeO | about 0.10 - 0.25 |
Er2O3 | about 0.50 - 3.0 |
B2O3 | about 0 - 12.0 |
Batch Ingredient | Parts by Wt. |
sand | about 70-73 |
soda ash | about 20-26 |
dolomite | about 16-19 |
limestone | about 5.5-6.8 |
boric acid | about 0.5-21 |
salt cake | about 0.2-0.7 |
rouge (Fe2O3) | about 0.5-0.8 |
titania | about 0.1-1.0 |
erbium oxide | about 0.5-3.0 |
Si (metal) | about 0.01-0.12 |
SiO | about 0.02-0.3 |
Claims (30)
- A glass comprised of a colorant portion consisting essentially of, by weight percent:
Fe2O3 (total iron) about 0.5-0.8% FeO about 0.1-0.25% Er2O3 about 0.5-3.0% TiO2 about 0.0-1.0% - A glass according to claim 1 wherein said glass is a soda-lime-silica glass.
- A glass according to claim 2 wherein said dominant wavelength and excitation purity are measured at a nominal thickness of said glass of about 3mm - 4mm.
- A glass according to claim 1, 2 or 3 wherein said glass is substantially free of selenium.
- A glass according to claim 4 wherein said glass is substantially free of cerium.
- A glass according to claim 5 wherein said glass is substantially free of nickel.
- A glass according to claim 6 wherein said glass is substantially free of cobalt.
- A glass according to claim 1 wherein said glass further includes by weight percent about 0.1 - 1.0% TiO2.
- A glass according to claim 1 wherein said glass further includes by weight percent about 0.25 - 1.0% B2O3.
- A glass according to claim 1 wherein said glass includes by weight percent:
Fe2O3 (total iron) about 0.6-0.8% FeO about 0.16-0.25% Er2O3 about 1.0-2.0%. - A glass according to claim 1 or 9 wherein said glass has the following characteristics when measured at a nominal thickness of 4mm:
- LTa:
- greater than or equal to about 70%
- UV:
- less than about 42%
- IR:
- less than about 37%.
- A glass according to claim 11 wherein said:
- LTa
- is equal to or greater than about 70%
- UV
- is less than about 39%
- IR
- is less than about 28%, and
- Ts
- is less than about 47%.
- A glass according to claim 12, wherein said glass when measured at a nominal thickness of 3mm - 4mm has a purity of about 0.2 - 4.5% and a dominant wavelength of 480nm - 550nm.
- A glass according to claim 1 wherein when measured at a nominal thickness of 4mm, said glass has the following characteristics according to Ill. C, 2° observer, CIE:
- L*
- about 86 - 91
- a*
- about -2.4 to +1.6
- b*
- about -5.0 to +2.0.
- A glass according to claim 14 wherein said characteristic according to Ill. C, 2° observer, CIE is:
- L*
- about 87 - 89
- a*
- about -0.5 to +1.0
- b*
- about -3.0 to -1.0.
- A glass composition comprising by weight percent:
Ingredient Wt. % SiO2 about 65 - 75 Na2O about 10 - 15 CaO about 1.5 - 15 MgO about 0 - 10 Al2O3 about 0 - 3 K2O about 0.1 - 1 SO3 about 0.1 - 0.3 TiO2 about 0 - 1.0 Fe2O3 about 0.50 - 0.80 FeO about 0.10 - 0.25 Er2O3 about 0.50 - 3.0 B2O3 about 0 - 12.0 - A glass composition according to claim 16, wherein, by weight percent:
Ingredient Wt. % TiO2 0.1 - 0.50 Fe2O3 (total iron) 0.55 - 0.80 FeO 0.16 - 0.25 Er2O3 1.0 - 2.0 - A glass composition according to claim 17 wherein said composition includes about 0.25 - 1.0% by weight B2O3.
- A glass article formed of the composition of claim 17 wherein said glass article when measured at a nominal thickness of about 1mm - 6mm, has a dominant wavelength of from about 435nm to less than about 570nm and an excitation purity of less than about 4.5%.
- A glass article formed of the composition of claim 18 wherein said glass article when measured at a nominal thickness of about 1mm - 6mm, has a dominant wavelength of 480-550nm and an excitation purity of 0.2-4.5%.
- A glass article according to claim 17, 18, 19 or 20 wherein said glass article is a component of an automotive window.
- A glass article according to claim 17, 18, 19, 20 or 21 wherein said glass article is a lens of an eyeglass or an architectural window.
- A method of making the glass of claim 1 comprising the steps of:a) forming at least two separate prebatch mixes which when mixed together form an overall batch mixture comprising:
Ingredient sand iron oxide erbium oxide SiO Ingredient iron oxide SiO sand b) mixing said first prebatch ingredients together separately from said remaining batch ingredients to form said first prebatch mix,c) mixing said remaining ingredients so as to form at least one other separate prebatch mix,d) mixing said prebatch mixes together to form said overall batch mixture,e) melting said overall batch mixture to form a glass therefrom, and thereafterf) forming said glass into said glass article. - A method according to claim 23 which includes the steps of:a) forming at least three separate prebatch mixes,b) separately mixing together the ingredients in each said prebatch mix and, thereafterc) mixing said at least three separate pre-mixed prebatch mixes to form said overall batch mixture, wherein one of said prebatch mixes comprises:
Ingredient sand dolomite limestone boric acid salt cake Ingredient soda ash titania erbium - A method according to claim 23 wherein said glass is a grey glass automotive window which when measured at a nominal thickness of about 1mm - 6mm, has a dominant wavelength of from about 435nm to less than about 570nm, an excitation purity of less than about 4.5%, an LTa equal to or greater than about 70%, an IR transmittance less than about 28%, and a UV transmittance less than 42%.
- A method according to claim 25 wherein said glass when said glass is measured at a nominal thickness of about 3mm - 4mm the glass has a dominant wavelength of from about 480mm to 550mm, an excitation purity of about 0.2 - 4.3%, an Lta of greater than about 70%, a UV less than about 38%, an IR less than about 28%, and a Ts less than about 47%.
- A method according to claim 23 wherein said overall batch mixture further includes:
Ingredient soda ash dolomite limestone boric acid salt cake. - A method according to claim 27 wherein said first prebatch mix consists essentially of:
Ingredient iron oxide as rouge metallic Si SiO sand. - A method according to claim 27 wherein said overall batch mixture further includes titania.
- A batch mixture capable of forming the glass of claims 1, 10, and 12 wherein said batch mixture includes about 0.01 - 0.3 wt.% SiO and about 0 - 0.12 wt.% metallic silicon.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US277749 | 1999-03-29 | ||
US09/277,749 US6235666B1 (en) | 1999-03-29 | 1999-03-29 | Grey glass composition and method of making same |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1041050A1 true EP1041050A1 (en) | 2000-10-04 |
EP1041050B1 EP1041050B1 (en) | 2007-02-14 |
Family
ID=23062194
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00105978A Expired - Lifetime EP1041050B1 (en) | 1999-03-29 | 2000-03-24 | Grey glass composition and method of making same |
Country Status (5)
Country | Link |
---|---|
US (2) | US6235666B1 (en) |
EP (1) | EP1041050B1 (en) |
CA (1) | CA2302560C (en) |
DE (1) | DE60033332T2 (en) |
ES (1) | ES2280157T3 (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002059052A1 (en) | 2001-01-23 | 2002-08-01 | Guardian Industries Corp. | Grey glass composition including erbium |
WO2002081395A1 (en) * | 2001-04-03 | 2002-10-17 | Guardian Industries Corp. | Grey glass composition including erbium |
US6498118B1 (en) | 2001-06-27 | 2002-12-24 | Guardian Industries Corp. | Grey glass composition including erbium and holmium |
WO2003027036A1 (en) * | 2001-09-26 | 2003-04-03 | Guardian Industries Corp. | Grey glass composition including erbium, holmium, and/or yttrium |
WO2004028990A1 (en) * | 2002-09-27 | 2004-04-08 | Ppg Industries Ohio, Inc. | Method for making float glass having reduced defect density |
WO2006091441A1 (en) * | 2005-02-23 | 2006-08-31 | Guardian Industries Corp. | Grey glass composition |
WO2007055940A2 (en) * | 2005-11-02 | 2007-05-18 | Ppg Industries Ohio, Inc. | Gray glass composition |
US7585801B2 (en) | 2005-11-02 | 2009-09-08 | Ppg Industries Ohio, Inc. | Gray glass composition |
WO2013039371A1 (en) * | 2011-09-14 | 2013-03-21 | Vidrio Plano De México, S.A. De C.V. | Neutral grey glass compositions |
Families Citing this family (47)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001067355A2 (en) * | 2000-03-07 | 2001-09-13 | American Express Travel Related Services Company, Inc. | System for facilitating a transaction |
US6672108B2 (en) | 2001-04-26 | 2004-01-06 | Guardian Industries Corp. | Method of making glass with reduced Se burnoff |
US7144837B2 (en) * | 2002-01-28 | 2006-12-05 | Guardian Industries Corp. | Clear glass composition with high visible transmittance |
US6610622B1 (en) * | 2002-01-28 | 2003-08-26 | Guardian Industries Corp. | Clear glass composition |
US7037869B2 (en) | 2002-01-28 | 2006-05-02 | Guardian Industries Corp. | Clear glass composition |
US7169722B2 (en) * | 2002-01-28 | 2007-01-30 | Guardian Industries Corp. | Clear glass composition with high visible transmittance |
US6953759B2 (en) * | 2002-08-26 | 2005-10-11 | Guardian Industries Corp. | Glass composition with low visible and IR transmission |
US6927186B2 (en) * | 2002-12-04 | 2005-08-09 | Guardian Industries Corp. | Glass composition including sulfides having low visible and IR transmission |
US7135425B2 (en) * | 2002-12-13 | 2006-11-14 | Guardian Industries Corp. | Grey glass composition |
US7151065B2 (en) * | 2003-07-21 | 2006-12-19 | Guardian Industries Corp. | Grey glass composition |
US7150820B2 (en) * | 2003-09-22 | 2006-12-19 | Semitool, Inc. | Thiourea- and cyanide-free bath and process for electrolytic etching of gold |
US7601660B2 (en) * | 2004-03-01 | 2009-10-13 | Guardian Industries Corp. | Clear glass composition |
US20050202951A1 (en) * | 2004-03-15 | 2005-09-15 | Guardian Industries Corp. | Method of making float glass |
US7937969B2 (en) * | 2004-08-26 | 2011-05-10 | Carty William M | Selective batching for boron-containing glasses |
US7700869B2 (en) * | 2005-02-03 | 2010-04-20 | Guardian Industries Corp. | Solar cell low iron patterned glass and method of making same |
US7625830B2 (en) * | 2005-02-10 | 2009-12-01 | Ppg Industries Ohio, Inc. | Blue glass composition |
US7700870B2 (en) * | 2005-05-05 | 2010-04-20 | Guardian Industries Corp. | Solar cell using low iron high transmission glass with antimony and corresponding method |
US7488538B2 (en) * | 2005-08-08 | 2009-02-10 | Guardian Industries Corp. | Coated article including soda-lime-silica glass substrate with lithium and/or potassium to reduce sodium migration and/or improve surface stability and method of making same |
US7538054B2 (en) * | 2005-08-09 | 2009-05-26 | Guardian Industries Corp. | Grey glass composition including erbium, neodymium and/or praseodymium |
US20070074757A1 (en) * | 2005-10-04 | 2007-04-05 | Gurdian Industries Corp | Method of making solar cell/module with porous silica antireflective coating |
US20070113881A1 (en) * | 2005-11-22 | 2007-05-24 | Guardian Industries Corp. | Method of making solar cell with antireflective coating using combustion chemical vapor deposition (CCVD) and corresponding product |
US8153282B2 (en) * | 2005-11-22 | 2012-04-10 | Guardian Industries Corp. | Solar cell with antireflective coating with graded layer including mixture of titanium oxide and silicon oxide |
US7557053B2 (en) * | 2006-03-13 | 2009-07-07 | Guardian Industries Corp. | Low iron high transmission float glass for solar cell applications and method of making same |
US8648252B2 (en) * | 2006-03-13 | 2014-02-11 | Guardian Industries Corp. | Solar cell using low iron high transmission glass and corresponding method |
US20080072956A1 (en) * | 2006-09-07 | 2008-03-27 | Guardian Industries Corp. | Solar cell with antireflective coating comprising metal fluoride and/or silica and method of making same |
US8637762B2 (en) * | 2006-11-17 | 2014-01-28 | Guardian Industries Corp. | High transmission glass ground at edge portion(s) thereof for use in electronic device such as photovoltaic applications and corresponding method |
US7767253B2 (en) * | 2007-03-09 | 2010-08-03 | Guardian Industries Corp. | Method of making a photovoltaic device with antireflective coating |
US8237047B2 (en) * | 2007-05-01 | 2012-08-07 | Guardian Industries Corp. | Method of making a photovoltaic device or front substrate for use in same with scratch-resistant coating and resulting product |
US20080295884A1 (en) * | 2007-05-29 | 2008-12-04 | Sharma Pramod K | Method of making a photovoltaic device or front substrate with barrier layer for use in same and resulting product |
US20090025426A1 (en) * | 2007-07-23 | 2009-01-29 | Guardian Industries Corp. | UV treated grey glass and method of making same |
US8445774B2 (en) * | 2007-07-26 | 2013-05-21 | Guardian Industries Corp. | Method of making an antireflective silica coating, resulting product, and photovoltaic device comprising same |
US8450594B2 (en) * | 2007-07-26 | 2013-05-28 | Guardian Industries Corp. | Method of making an antireflective silica coating, resulting product and photovoltaic device comprising same |
US7932198B2 (en) * | 2007-09-04 | 2011-04-26 | Guardian Industries Corp. | Grey glass composition |
US7863208B2 (en) * | 2007-09-04 | 2011-01-04 | Guardian Industries Corp. | Grey glass composition |
US20090075092A1 (en) * | 2007-09-18 | 2009-03-19 | Guardian Industries Corp. | Method of making an antireflective silica coating, resulting product, and photovoltaic device comprising same |
US20090101209A1 (en) * | 2007-10-19 | 2009-04-23 | Guardian Industries Corp. | Method of making an antireflective silica coating, resulting product, and photovoltaic device comprising same |
US8114472B2 (en) * | 2008-01-08 | 2012-02-14 | Guardian Industries Corp. | Method of making a temperable antiglare coating, and resulting products containing the same |
US20090181256A1 (en) * | 2008-01-14 | 2009-07-16 | Guardian Industries Corp. | Methods of making silica-titania coatings, and products containing the same |
US8668961B2 (en) * | 2008-07-31 | 2014-03-11 | Guardian Industries Corp. | Titania coating and method of making same |
US20100122728A1 (en) * | 2008-11-17 | 2010-05-20 | Fulton Kevin R | Photovoltaic device using low iron high transmission glass with antimony and reduced alkali content and corresponding method |
US8617641B2 (en) * | 2009-11-12 | 2013-12-31 | Guardian Industries Corp. | Coated article comprising colloidal silica inclusive anti-reflective coating, and method of making the same |
US9272949B2 (en) | 2010-07-09 | 2016-03-01 | Guardian Industries Corp. | Coated glass substrate with heat treatable ultraviolet blocking characteristics |
US11261122B2 (en) | 2013-04-15 | 2022-03-01 | Vitro Flat Glass Llc | Low iron, high redox ratio, and high iron, high redox ratio, soda-lime-silica glasses and methods of making same |
US20140309099A1 (en) | 2013-04-15 | 2014-10-16 | Ppg Industries Ohio, Inc. | Low iron, high redox ratio, and high iron, high redox ratio, soda-lime-silica glasses and methods of making same |
US10753883B2 (en) | 2017-06-07 | 2020-08-25 | Guardian Glass, LLC | Method and system for detecting inclusions in float glass |
US10481097B1 (en) | 2018-10-01 | 2019-11-19 | Guardian Glass, LLC | Method and system for detecting inclusions in float glass based on spectral reflectance analysis |
WO2023248843A1 (en) * | 2022-06-20 | 2023-12-28 | Agc株式会社 | Alkali borosilicate glass, curved glass, laminated glass, architectural window glass and vehicle window glass |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS593043A (en) * | 1982-06-30 | 1984-01-09 | Shoei Kogyo Kk | Reducible frit for regulating color development |
JPH04280834A (en) * | 1991-03-08 | 1992-10-06 | Nippon Sheet Glass Co Ltd | Colored glass |
FR2682372A1 (en) * | 1991-10-11 | 1993-04-16 | Nippon Sheet Glass Co Ltd | COMPOSITION OF GLASS PANELS FOR VEHICLES. |
US5411922A (en) * | 1993-12-27 | 1995-05-02 | Ford Motor Company | Neutral gray-green low transmittance heat absorbing glass |
US5569630A (en) * | 1992-10-04 | 1996-10-29 | Landa; Leonid | Composites for glass |
EP0849233A1 (en) * | 1996-12-19 | 1998-06-24 | Nippon Sheet Glass Co., Ltd. | Ultraviolet and infrared radiation absorbing and low transmittance glass |
GB2325927A (en) * | 1997-06-07 | 1998-12-09 | Pilkington Plc | Grey and bronze glass compositions for absorbing uv |
Family Cites Families (44)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1634182A (en) | 1925-05-11 | 1927-06-28 | Chance Brothers & Co Ltd | Colorless crookes glass |
US2099602A (en) | 1934-02-21 | 1937-11-16 | Fischer Hellmuth | Luminescent glass |
US2701208A (en) | 1950-11-14 | 1955-02-01 | Univ Ohio State Res Found | Glasses |
US2691599A (en) | 1950-11-14 | 1954-10-12 | Univ Ohio State Res Found | Glasses |
US2805166A (en) | 1954-01-18 | 1957-09-03 | Loffler Johannes | Glasses containing oxides of rare earth metals |
NL6914441A (en) | 1968-10-04 | 1970-04-07 | ||
US3652303A (en) * | 1970-01-26 | 1972-03-28 | Ppg Industries Inc | Heat absorbing blue soda-lime-silica glass |
US3941171A (en) | 1973-07-05 | 1976-03-02 | Ims Limited | Fluid transfer device |
JPS5243649B2 (en) | 1974-03-09 | 1977-11-01 | ||
SU555061A1 (en) * | 1974-04-29 | 1977-04-25 | Предприятие П/Я В-2268 | Glass |
US3960754A (en) | 1974-08-01 | 1976-06-01 | American Optical Corporation | Multi-wavelength optical filter |
US3959171A (en) | 1974-08-01 | 1976-05-25 | American Optical Corporation | Optical filter for neodymium laser light |
FR2293328A1 (en) | 1974-12-03 | 1976-07-02 | Saint Gobain | TINTED WINDOWS FOR MOTOR VEHICLES |
JPS5385813A (en) * | 1976-12-30 | 1978-07-28 | Hoya Glass Works Ltd | Spectacle glass having glareeprotection effect |
DE3135312A1 (en) | 1980-11-27 | 1982-07-01 | Licentia Patent-Verwaltungs-Gmbh, 6000 Frankfurt | "OPTICAL BRANCH" |
DE3206958C2 (en) | 1982-02-26 | 1986-09-18 | Schott Glaswerke, 6500 Mainz | Phototropic glass with a refractive index? 1.59, an Abbe number? 44 and a density ≦ 3.0 g / cm? 3? |
JPS618365A (en) | 1984-06-22 | 1986-01-16 | Fuji Xerox Co Ltd | Transfer type thermal recorder |
JPS6183645A (en) * | 1984-09-28 | 1986-04-28 | Hoya Corp | Glass for lens of color contrast spectacles |
US4769347A (en) | 1986-01-06 | 1988-09-06 | Schott Glass Technologies, Inc. | Contrast enhancement filter glass for color CRT displays |
US5039631A (en) | 1990-01-11 | 1991-08-13 | Schott Glass Technologies, Inc. | Strengthenable, high non-nd lanthanoid-containing glasses |
DE69106795T2 (en) | 1990-02-05 | 1995-09-07 | Furukawa Electric Co Ltd | QUARTZ GLASS DOPED WITH A RARE EARTH ELEMENT AND METHOD FOR THE PRODUCTION THEREOF. |
US5061659A (en) | 1990-08-07 | 1991-10-29 | Schott Glass Technologies, Inc. | Contrast enhancement filter glass useful for color CRT displays |
US5036025A (en) | 1990-10-02 | 1991-07-30 | Hoya Optics Inc. | Infrared absorbing green glass |
DE4203578C2 (en) * | 1991-02-08 | 2000-10-19 | Nippon Sheet Glass Co Ltd | Glass for vehicles |
JP2571646B2 (en) | 1991-03-06 | 1997-01-16 | ホーヤ株式会社 | Ivory-colored zirconia sintered body and its use |
US5263858A (en) | 1991-03-06 | 1993-11-23 | Hoya Corporation | Ivory-colored zirconia sintered body, process for its production and its use |
US5190896A (en) | 1991-07-22 | 1993-03-02 | Schott Glass Technologies, Inc. | Contrast enhancement in glass |
FR2682101B1 (en) | 1991-10-03 | 1994-10-21 | Saint Gobain Vitrage Int | COLORED GLASS COMPOSITION FOR MAKING WINDOWS. |
US5206189A (en) | 1991-10-25 | 1993-04-27 | Instituto Guido Donegani S.P.A. | Sol-gel method for the preparation of monolithic multicomponent oxide glasses |
US5318316A (en) | 1992-02-12 | 1994-06-07 | Shurtleff David P | Cart for vertically oriented longitudinally extending objects |
EP0561337A1 (en) | 1992-03-18 | 1993-09-22 | Central Glass Company, Limited | Bronze-colored infrared and ultraviolet radiation absorbing glass |
EP0565882B1 (en) | 1992-03-19 | 1997-06-04 | Central Glass Company, Limited | Neutral gray-colored infrared and ultraviolet radiation absorbing glass |
JP3411067B2 (en) | 1993-08-27 | 2003-05-26 | 株式会社住田光学ガラス | Wavelength up-converting transparent glass-ceramics and method for producing the same |
US5413971A (en) | 1993-09-14 | 1995-05-09 | Mcpherson; Donald M. | Laser absorbing filter glass |
JPH07109147A (en) * | 1993-10-15 | 1995-04-25 | Nippon Sheet Glass Co Ltd | Uv light-absorbing gray glass |
CZ279603B6 (en) | 1993-11-03 | 1995-05-17 | Vysoká Škola Chemicko-Technologická | Crystal lead-free glass with refractive index greater than 1.52 |
NZ264881A (en) | 1993-11-16 | 1995-09-26 | Ppg Industries Inc | Grey glass containing iron and cobalt oxides |
US5446007A (en) | 1994-05-10 | 1995-08-29 | Schott Glass Technologies, Inc. | Brown contrast enhancement glass |
FR2721599B1 (en) * | 1994-06-23 | 1996-08-09 | Saint Gobain Vitrage | Glass composition intended for the manufacture of glazing. |
CA2201576A1 (en) | 1996-04-17 | 1997-10-17 | James Edward Dickinson, Jr. | Rare earth doped oxyhalide laser glass |
US6413893B1 (en) | 1996-07-02 | 2002-07-02 | Ppg Industries Ohio, Inc. | Green privacy glass |
ES2157499T3 (en) | 1996-07-02 | 2001-08-16 | Ppg Ind Ohio Inc | INSULATION GREEN GLASS. |
JPH10101369A (en) | 1996-10-01 | 1998-04-21 | Nippon Sheet Glass Co Ltd | Ultraviolet ray and infrared ray absorbing glass |
US5858869A (en) * | 1997-06-03 | 1999-01-12 | Industrial Technology Research Institute | Method for fabricating intermetal dielectric insulation using anisotropic plasma oxides and low dielectric constant polymers |
-
1999
- 1999-03-29 US US09/277,749 patent/US6235666B1/en not_active Expired - Lifetime
-
2000
- 2000-03-22 CA CA002302560A patent/CA2302560C/en not_active Expired - Fee Related
- 2000-03-24 ES ES00105978T patent/ES2280157T3/en not_active Expired - Lifetime
- 2000-03-24 EP EP00105978A patent/EP1041050B1/en not_active Expired - Lifetime
- 2000-03-24 DE DE60033332T patent/DE60033332T2/en not_active Expired - Lifetime
-
2001
- 2001-02-23 US US09/791,064 patent/US6403509B2/en not_active Expired - Lifetime
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS593043A (en) * | 1982-06-30 | 1984-01-09 | Shoei Kogyo Kk | Reducible frit for regulating color development |
JPH04280834A (en) * | 1991-03-08 | 1992-10-06 | Nippon Sheet Glass Co Ltd | Colored glass |
FR2682372A1 (en) * | 1991-10-11 | 1993-04-16 | Nippon Sheet Glass Co Ltd | COMPOSITION OF GLASS PANELS FOR VEHICLES. |
US5569630A (en) * | 1992-10-04 | 1996-10-29 | Landa; Leonid | Composites for glass |
US5411922A (en) * | 1993-12-27 | 1995-05-02 | Ford Motor Company | Neutral gray-green low transmittance heat absorbing glass |
EP0849233A1 (en) * | 1996-12-19 | 1998-06-24 | Nippon Sheet Glass Co., Ltd. | Ultraviolet and infrared radiation absorbing and low transmittance glass |
GB2325927A (en) * | 1997-06-07 | 1998-12-09 | Pilkington Plc | Grey and bronze glass compositions for absorbing uv |
Non-Patent Citations (2)
Title |
---|
"CHEMICAL ABSTRACTS + INDEXES,US,AMERICAN CHEMICAL SOCIETY. COLUMBUS", CHEMICAL ABSTRACTS + INDEXES,US,AMERICAN CHEMICAL SOCIETY. COLUMBUS, vol. 118, no. 8, 22 February 1993 (1993-02-22), pages 358, XP000352817, ISSN: 0009-2258 * |
DATABASE WPI Section Ch Week 198407, Derwent World Patents Index; Class L01, AN 1984-040298, XP002141977 * |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002059052A1 (en) | 2001-01-23 | 2002-08-01 | Guardian Industries Corp. | Grey glass composition including erbium |
US6521558B2 (en) | 2001-01-23 | 2003-02-18 | Guardian Industries Corp. | Grey glass composition including erbium |
US6573207B2 (en) | 2001-01-23 | 2003-06-03 | Guardian Industries Corp. | Grey glass composition including erbium |
WO2002081395A1 (en) * | 2001-04-03 | 2002-10-17 | Guardian Industries Corp. | Grey glass composition including erbium |
US6498118B1 (en) | 2001-06-27 | 2002-12-24 | Guardian Industries Corp. | Grey glass composition including erbium and holmium |
WO2003002474A1 (en) * | 2001-06-27 | 2003-01-09 | Guardian Industries Corp. | Grey glass composition including erbium and holmium, or at least three different lanthanides |
WO2003027036A1 (en) * | 2001-09-26 | 2003-04-03 | Guardian Industries Corp. | Grey glass composition including erbium, holmium, and/or yttrium |
US6716780B2 (en) | 2001-09-26 | 2004-04-06 | Guardian Industries Corp. | Grey glass composition including erbium, holmium, and/or yttrium |
WO2004028990A1 (en) * | 2002-09-27 | 2004-04-08 | Ppg Industries Ohio, Inc. | Method for making float glass having reduced defect density |
US7162892B2 (en) | 2002-09-27 | 2007-01-16 | Pgg Industries Ohio, Inc. | Method for making float glass having reduced defect density |
US7414000B2 (en) * | 2002-09-27 | 2008-08-19 | Ppg Industries Ohio, Inc. | Method for making float glass having reduced defect density |
WO2006091441A1 (en) * | 2005-02-23 | 2006-08-31 | Guardian Industries Corp. | Grey glass composition |
US7622410B2 (en) | 2005-02-23 | 2009-11-24 | Guardian Industries Corp. | Grey glass composition |
WO2007055940A2 (en) * | 2005-11-02 | 2007-05-18 | Ppg Industries Ohio, Inc. | Gray glass composition |
WO2007055940A3 (en) * | 2005-11-02 | 2007-07-05 | Ppg Ind Ohio Inc | Gray glass composition |
US7585801B2 (en) | 2005-11-02 | 2009-09-08 | Ppg Industries Ohio, Inc. | Gray glass composition |
US7666806B2 (en) | 2005-11-02 | 2010-02-23 | Ppg Industries Ohio, Inc. | Gray glass composition |
WO2013039371A1 (en) * | 2011-09-14 | 2013-03-21 | Vidrio Plano De México, S.A. De C.V. | Neutral grey glass compositions |
US9115021B2 (en) | 2011-09-14 | 2015-08-25 | Vidrio Plano De Mexico, S.A. De C.V. | Neutral grey glass compositions |
Also Published As
Publication number | Publication date |
---|---|
US20010006927A1 (en) | 2001-07-05 |
CA2302560C (en) | 2008-05-27 |
ES2280157T3 (en) | 2007-09-16 |
CA2302560A1 (en) | 2000-09-29 |
DE60033332T2 (en) | 2007-11-22 |
US6403509B2 (en) | 2002-06-11 |
US6235666B1 (en) | 2001-05-22 |
EP1041050B1 (en) | 2007-02-14 |
DE60033332D1 (en) | 2007-03-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1041050B1 (en) | Grey glass composition and method of making same | |
US6521558B2 (en) | Grey glass composition including erbium | |
US6573207B2 (en) | Grey glass composition including erbium | |
US6498118B1 (en) | Grey glass composition including erbium and holmium | |
US6716780B2 (en) | Grey glass composition including erbium, holmium, and/or yttrium | |
EP0802168B1 (en) | A substantially nickel-free soda-lime-silica glass exhibiting low light transmittance in the U.V., visible and I.R. energy ranges | |
EP0821659B1 (en) | Colored glass compositions | |
US7325417B2 (en) | Glass composition with low visible and IR transmission | |
EP0648195B1 (en) | Glass composition | |
EP1132350A1 (en) | Infrared and ultraviolet radiation absorbing blue glass composition | |
EP3081542A1 (en) | Uv-absorbing glass article | |
US7538054B2 (en) | Grey glass composition including erbium, neodymium and/or praseodymium | |
JPH11512694A (en) | Glass with neutral color and low radiation transmittance | |
US7135425B2 (en) | Grey glass composition | |
US6672108B2 (en) | Method of making glass with reduced Se burnoff | |
JP2001019470A (en) | Glass with dark gray color | |
JP3431395B2 (en) | UV absorbing gray color glass | |
JPH0948635A (en) | Ultraviolet and infrared rays-absorving glass | |
MXPA97002739A (en) | Low transmitt glass |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): DE ES FR GB IT |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
17P | Request for examination filed |
Effective date: 20010103 |
|
AKX | Designation fees paid |
Free format text: DE ES FR GB IT |
|
17Q | First examination report despatched |
Effective date: 20020522 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE ES FR GB IT |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 60033332 Country of ref document: DE Date of ref document: 20070329 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2280157 Country of ref document: ES Kind code of ref document: T3 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20071115 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20140317 Year of fee payment: 15 Ref country code: ES Payment date: 20140326 Year of fee payment: 15 Ref country code: IT Payment date: 20140325 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20140327 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20140327 Year of fee payment: 15 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 60033332 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20150324 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150324 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20151130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20151001 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150324 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150331 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20160428 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150325 |